Stabilized body care products, household products, textiles and fabrics

ABSTRACT

Disclosed are stabilized body care products, household products, textiles and fabrics which comprise certain dialkylhydroxyamine stabilizers, dialkylhydroxylamine stabilizer salts, nitrone stabilizers or amine oxide stabilizers. Dyed products and articles are effectively stabilized against color degradation. The products are for example skin-care products, hair-care products, dentifrices, cosmetics, laundry detergents and fabric softeners, non-detergent based fabric care products, household cleaners and textile-care products.

This application is a continuation of application Ser. No. 10/970,112,filed Oct. 21, 2004, which claims benefit under 35 USC 119(e) of U.S.provisional application No. 60/515,889, filed Oct. 30, 2003, each ofwhich is herein incorporated by reference.

The present invention relates to the use of selecteddialkylhydroxylamine stabilizers, dialkylhydroxylamine stabilizer salts,nitrone stabilizers or amine oxide stabilizers for the protection ofbody care products, household products, textiles and fabrics against thedeleterious effects of light, heat and oxygen.

The stabilized compositions for example comprise dyes that arestabilized against color change.

WO 00/25730 and WO 00/25731 are aimed at the stabilization of body careand household products.

WO 01/07550 teaches the treatment of fabric with hindered aminestabilizers.

U.S. Pat. No. 6,599,326 teaches the stabilization of pulp or paper withdialkylhydroxylamines or substituted dialkylhydroxylamines or theirsalts.

U.S. Pat. No. 4,898,901 discloses nitrone stabilizers.

U.S. Pat. Nos. 5,081,300, 5,844,029 and 5,922,794 disclose amine oxidestabilizers.

DETAILED DISCLOSURE

The present invention pertains to a stabilized composition comprising

(a) a body care product, household product, textile or fabric and

(b) an effective stabilizing amount of at least one compound selectedfrom the group consisting of

-   -   (i) the dialkylhydroxylamine stabilizers,    -   (ii) the dialkylhydroxylamine stabilizer salts,    -   (iii) the nitrone stabilizers and    -   (iv) the amine oxide stabilizers.

Dialkylhydroxylamine stabilizers, for example N,N,-dialkylhydroxylaminesand N,N-dibenzylhydroxylamine, are well known as useful stabilizers fora variety of polymeric substrates as is taught for example in U.S. Pat.Nos. 4,590,231, 4,668,721, 4,782,105, 4,876,300 and 5,013,510, therelevant parts of which are incorporated herein by reference.

U.S. Pat. Nos. 4,649,221 and 4,703,073 teach the use ofpolyhydroxylamine compounds and alkylated N,N-dibenzylhydroxylaminederivatives, respectively, towards stabilizing polyolefins. Thedisclosures of these U.S. patents are also hereby incorporated byreference.

Ester, amide or thio substituted N,N-dialkylhydroxylamines are describedin U.S. Pat. Nos. 4,612,393, 4,720,517 and 5,019,285, the relevantdisclosures of which are also hereby incorporated by reference.

For example, the present dialkylhydroxylamine stabilizers are thosedisclosed in the above mentioned U.S. patents, and are for instance ofthe formulaR₁R₂N—OH

where

R₁ is alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atomsor aralkyl of 7 to 9 carbon atoms; or R₁ is said alkyl, cycloalkyl oraralkyl substituted by one to six alkyl of 1 to 12 carbon atoms,halogen, cyano, E₁O—, E₁CO—, E₁OCO—, E₁COO—, E₁S—, E₁SO—, E₁SO₂—, —NH₂,—NHE₁, —NE₁E₂, —PO(OE₁)(OE₂) or —OPO(OE₁)(OE₂) groups;

R₂ is hydrogen or independently has the same meaning as R₁, where atleast one of R₁ and R₂ contains a hydrogen alpha to the —NOH moiety; or

R₁ and R₂ together form a C₂₋₁₂heterocyclic ring which contains at leastone carbon substituted hydrogen alpha to the —NOH moiety, where saidC₂₋₁₂heterocyclic ring is unsubstituted or is substituted by one tothree three alkyl of 1 to 12 carbon atoms, halogen, cyano, E₁O—, E₁CO—,E₁OCO—, E₁COO—, E₁S—, E₁SO—, E₁SO₂—, —NH₂, —NHE₁, —NE₁E₂, —PO(OE₁)(OE₂)or —OPO(OE₁)(OE₂) groups; or where said C₂₋₁₂heterocyclic ring isinterrupted by one to three —O—, —NE₁—, —CO—, —CONE₁—, —S—, —SO—, —SO₂—,—COO—, —PO₃— or —PO₄E₁ groups; or where said heterocyclic ring is bothsubstituted and interrupted by said groups; and

E₁ and E₂ independently are hydrogen, alkyl of 1 to 4 carbon atoms oralkyl of 1 to 4 carbon atoms substituted by one to three hydroxylgroups; or E₁ and E₂ independently are an oligomer of poly(ethyleneglycol) or poly(propylene glycol) terminated by hydroxyl, methoxy,acetate or propionate, where the oligomer has a molecular weight up toabout 500.

The phrase “where at least one of R₁ and R₂ contains a hydrogen alpha tothe —NOH moiety” means that the present dialkylhydroxylamines are notdi-tert-alkylhydroxylamines.

The present dialkylhydroxylamine stabilizers are, for example,N,N-dihydrocarbylhydroxylamines wherein R₁ and R₂ are independentlybenzyl, methyl, ethyl, octyl, lauryl, dodecyl, tetradecyl, hexadecyl,heptadecyl or octadecyl, or wherein R₁ and R₂ are each the alkyl mixturefound in hydrogenated tallow amine.

The present dialkylhydroxylamine stabilizers are, for example,N,N-dihydrocarbylhydroxylamines selected from the group consisting ofN,N-dibenzylhydroxylamine, N,N-dimethylhydroxylamine,N,N-diethylhydroxylamine, N,N-bis(2-hydroxypropyl)hydroxylamine,N,N-bis(3-hydroxypropyl)hydroxylamine,N,N-bis(2-carboxyethyl)hydroxylamine,N,N-bis(benzylthiomethyl)hydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-didodecylhydroxylamine,N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine,N,N-dioctadecylhydroxylamine, N-hexadecyl-N-tetradecylhydroxylamine,N-hexadecyl-N-heptadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine,N-methyl-N-octadecylhydroxylamine, N,N-di(hydrogenatedtallow)hydroxylamine,

For example, the present dialkylhydroxylamine stabilizers areN,N-diethylhydroxylamine, N,N-bis(2-hydroxypropyl)hydroxylamine,N,N-bis(3-hydroxypropyl)hydroxylamine or N,N-dibenzylhydroxylamine orthe N,N-di(alkyl)hydroxylamine produced by the direct oxidation ofN,N-di(hydrogenated tallow)amine. The last named dialkylhydroxylamine,that is N,N-di(hydrogenated tallow)hydroxylamine, is as prepared in theworking Examples of U.S. Pat. No. 5,013,510.

The dialkylhydroxylamine stabilizer salts are inorganic or organic acidsalts of the present dialkylhydroxylamine stabilizers. For example, thedialkylhydroxylamine stabilizer salts are of the formula(R₁R₂N—OH).(HY)

where

R₁ and R₂ are as defined for the dialkylhydroxylamine stabilizers, and

HY is an inorganic or organic acid.

For example, Y is phosphate, phosphonate, carbonate, bicarbonate,nitrate, chloride, bromide, bisulfite, sulfite, bisulfate, sulfate,borate, formate, acetate, benzoate, citrate, oxalate, tartrate,acrylate, polyacrylate, fumarate, maleate, itaconate, glycolate,gluconate, malate, mandelate, tiglate, ascorbate, polymethacrylate, acarboxylate of nitrilotriacetic acid (NTA),diethylenetriaminepentamethylenephosphonic acid (DTPMPA),hydroxyethylethylenediaminetriacetic acid (HEDTA),ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaaceticacid (DTPA), diethylenediaminetetraacetic acid or ofdiethylenetriaminepentaacetic acid, an alkylsulfonate or anarylsulfonate.

For instance, when HY is hydrochloric acid, Y is chloride and thedialkylhydroxylamine salt is a dialkylhydroxylammonium chloride salt.

For example, Y is chloride, bisulfate, sulfate, phosphate, nitrate,ascorbate, formate, acetate, benzoate, oxalate, citrate, a carboxylateof ethylenediaminetetraacetic acid or of diethylenetriaminepentaaceticacid or polyacrylate, for instance Y is chloride, bisulfate or citrate.

For example, the present dialkylhydroxylamine stabilizer salts are saltsof the specific dialkylhydroxylamine stabilizers disclosed above.

For example, the present dialkylhydroxylamine stabilizer salts aretris(N,N-diethylhydroxylammonium) citrate ortris(N,N-dibenzylhydroxylammonium) citrate.

The nitrone stabilizers may be for example those as described in U.S.Pat. No. 4,898,901, which is hereby incorporated by reference.

The nitrone stabilizers are for example of the formula

wherein

R₁ is alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atomsor aralkyl of 7 to 9 carbon atoms; or R1 is said alkyl, cycloalkyl oraralkyl substituted by one to six alkyl of 1 to 12 carbon atoms,halogen, cyano, E₁O—, E₁CO—, E₁OCO—, E₁COO—, E₁S—, E₁SO—, E₁SO₂—, —NH₂,—NHE₁, —NE₁E₂, —PO(OE₁)(OE₂) or —OPO(OE₁)(OE₂) groups;

R₂ is hydrogen or independently has the same meaning as R₁; or

R₁ and R₂ together form a C₂₋₁₂heterocyclic ring which is unsubstitutedor is substituted by one to three three alkyl of 1 to 12 carbon atoms,halogen, cyano, E₁O—, E₁CO—, E₁OCO—, E₁COO—, E₁S—, E₁SO—, E₁SO₂—, —NH₂,—NHE₁, —NE₁E₂, —PO(OE₁)(OE₂) or —OPO(OE₁)(OE₂) groups; or where saidC₂₋₁₂heterocyclic ring is interrupted by one to three —O—, —NE₁—, —CO—,—CONE₁—, —S—, —SO—, —SO₂—, —COO—, —PO₃— or —PO₄E₁ groups; or where saidheterocyclic ring is both substituted and interrupted by said groups;

E₁ and E₂ independently are hydrogen, alkyl of 1 to 4 carbon atoms oralkyl of 1 to 4 carbon atoms substituted by one to three hydroxylgroups; or E₁ and E₂ independently are an oligomer of poly(ethyleneglycol) or poly(propylene glycol) terminated by hydroxyl, methoxy,acetate or propionate, where the oligomer has a molecular weight up toabout 500; and

R₃ independently has the same meaning as R₁.

The nitrone stabilizers may be the corresponding oxidation products ofthe dialkylhydroxylamine stabilizers. That is to say, the nitronestabilizers may be nitrone analogues of the present dialkylhydroxylaminestabilizers. The nitrone stabilizers are for example,N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone,N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone,N-tetradecyl-α-tridcylnitrone, N-hexadecyl-α-pentadecylnitrone,N-octadecyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone,N-ocatadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone,N-octadecyl-α-hexadecylnitrone, N-methyl-α-heptadecylnitrone and thenitrone derived from N,N-di(hydrogenated tallow)hydroxylamine.

The amine oxide stabilizers are for example those disclosed in U.S. Pat.Nos. 5,081,300, 5,162,408, 5,844,029, 5,880,191 and 5,922,794, therelevant parts of each incorporated herein by reference.

The amine oxide stabilizers are for example saturated tertiary amineoxides as represented by the formula:

wherein

R₁ is alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atomsor aralkyl of 7 to 9 carbon atoms; or R₁ is said alkyl, cycloalkyl oraralkyl substituted by one to six alkyl of 1 to 12 carbon atoms,halogen, cyano, E₁O—, E₁CO—, E₁OCO—, E₁COO—, E₁S—, E₁SO—, E₁SO₂—, —NH₂,—NHE₁, —NE₁E₂, —PO(OE₁)(OE₂) or —OPO(OE₁)(OE₂) groups;

R₂ is hydrogen or independently has the same meaning as R₁; or

R₁ and R₂ together form a C₂₋₁₂heterocyclic ring which is unsubstitutedor is substituted by one to three three alkyl of 1 to 12 carbon atoms,halogen, cyano, E₁O—, E₁CO—, E₁OCO—, E₁COO—, E₁S—, E₁SO—, E₁SO₂—, —NH₂,—NHE₁, —NE₁E₂, —PO(OE,)(OE₂) or —OPO(OE,)(OE₂) groups; or where saidC₂₋₁₂heterocyclic ring is interrupted by one to three —O—, —NE₁—, —CO—,—CONE₁—, —S—, —SO—, —SO₂—, —COO—, —PO₃— or —PO₄E₁ groups; or where saidheterocyclic ring is both substituted and interrupted by said groups;

E₁ and E₂ independently are hydrogen, alkyl of 1 to 4 carbon atoms oralkyl of 1 to 4 carbon atoms substituted by one to three hydroxylgroups; or E₁ and E₂ independently are an oligomer of poly(ethyleneglycol) or poly(propylene glycol) terminated by hydroxyl, methoxy,acetate or propionate, where the oligomer has a molecular weight up toabout 500; and

R₃ independently has the same meaning as R₁;

wherein at least one of R₁, R₂ and R₃ contains a β carbon-hydrogen bond.

Examples of amine oxide stabilizers are where R₁ and R₂ areindependently benzyl or substituted benzyl. It is also possible for eachof R₁, R₂, and R₃ to be the same residue. R₁ and R₂ may alsoindependently be alkyl groups of 8 to 26 carbon atoms, for example alkylgroups of 10 to 26 carbon atoms. R₃ may be an alkyl group of 1 to 22carbon atoms, for example methyl or substituted methyl. Also, thepresent amine oxides include those wherein R₁, R₂, and R₃ are the samealkyl groups of 6 to 36 carbon atoms.

The amine oxide stabilizer is for example Genox™ EP, a di(C₁₆-C₁₈)alkylmethyl amine oxide, CAS# 204933-93-7.

Alkyl groups, including alkyl groups of the various substituent groups,are linear or are branched.

Alkyl is for example methyl, ethyl, propyl such as n- or isopropyl,butyl such as n-, iso-, sec- and tert-butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl or octadecyl.

Aryl is C₆-C₁₂aryl, for example phenyl or naphthyl.

Cycloalkyl is for example, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl.

Aralkyl is for example phenylalkyl, which is alkyl substituted byphenyl. Examples are benzyl, α-methylbenzyl, and α-cumyl.

Alkenyl is ethylenically unsaturated alkyl, for example allyl, ethenyl,propenyl, butenyl.

Alkyl groups substituted by hydroxy are for example hydroxyethyl,di-hydroxyethyl, hydroxypropyl, di-hydroxypropyl, hydroxybutyl,hydroxypentyl or hydroxyhexyl.

Halogen is for example chloro, fluoro or bromo.

C₂₋₁₂heterocyclic rings are for example 5- or 6-membered rings such as

The present compositions may comprise further traditional additives, forexample ultraviolet (UV) light absorbers and antioxidants.

Accordingly, the present invention further pertains to a stabilizedcomposition comprising

(a) a body care product, household product, textile or fabric,

(b) an effective stabilizing amount of at least one compound selectedfrom the group consisting of

-   -   (i) the dialkylhydroxylamine stabilizers,    -   (ii) the dialkylhydroxylamine stabilizer salts,    -   (iii) the nitrone stabilizers and    -   (iv) the amine oxide stabilizers and

(c) at least one compound selected from the group consisting of theultraviolet light absorbers, antioxidants, tocopherol, tocopherolacetate, hindered amine light stabilizers, complex formers, opticalbrighteners, surfactants and polyorganosiloxanes.

The additional additives of present component (c) are for example thosedisclosed in co-pending U.S. application Ser. Nos. 09/830,788, filed May1, 2001 and 09/830,787, filed May 1, 2001. The disclosures of theseco-pending applications are hereby incorporated by reference. Theseapplications are published as WO 00/25730 and WO 00/25731.

The UV (ultraviolet light) absorbers are for example selected from groupconsisting of the 2H-benzotriazoles, the s-triazines, the benzophenones,the α-cyanoacrylates, the oxanilides, the benzoxazinones, the benzoatesand the α-alkyl cinnamates.

The UV absorbers are for example

-   -   2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine;    -   2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;    -   2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine;    -   2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine;    -   2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;    -   2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;    -   2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;    -   2-[2-hydroxy-4-(2-hydroxy-3-tridecyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;    -   5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;    -   2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;    -   5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;    -   bis-(3-(2H-benzotriazol-2-yl)-2-hydroxy-5-tert-octyl)methane;    -   2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;    -   2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;    -   2-(2-hydroxy-3,5-di-a-cumylphenyl)-2H-benzotriazole;    -   2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole;    -   2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;    -   3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesulfonic        acid monosodium salt;    -   3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinnamic        acid and sodium salt;    -   12-hydroxy-3,6,9-trioxadodecyl        3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinnamate;    -   octyl        3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinnamate;    -   4,6-bis(2,4-dimethylphenyl)-2-(4-(3-dodecyloxy*-2-hydroxypropoxy)-2-hydroxyphenyl)-s-triazine        (*is mixture of C₁₂₋₁₄oxy isomers);    -   4,6-bis(2,4-dimethylphenyl)-2-(4-octyloxy-2-hydroxyphenyl)-s-triazine;    -   2,4-dihydroxybenzophenone;    -   2,2′-dihydroxy-4,4′-dimethoxy-5,5′-disulfobenzophenone, disodium        salt;    -   2-hydroxy-4-octyloxybenzophenone;    -   2-hydroxy-4-dodecyloxybenzophenone;    -   2,4-dihydroxybenzophenone;    -   2,2′,4,4′-tetrahydroxybenzophenone;    -   4-aminobenzoic acid;    -   2,3-dihydroxypropyl-4-aminobenzoic acid;    -   3-(4-imidazolyl)acrylic acid;    -   2-phenyl-5-benzimidazole sulfonic acid;    -   N,N,N-trimethyl-α-(2-oxo-3-bornylidene)-p-toluidinium methyl        sulfate;    -   5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid, sodium salt;    -   3-(4-benzoyl-3-hydroxyphenoxy)-2-hydroxy-N,N,N-trimethyl-1-propanaminium        chloride;    -   3-[4-(2H-        benzotriazol-2-yl)-3-hydroxyphenoxy]-2-hydroxy-N,N,N-trimethyl-1-propanaminium,        chloride;    -   2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole; and    -   2,2′-dihydroxy-4,4′-dimethoxybenzophenone (Uvinul® 3049).

For instance, suitable UV absorbers are selected from

-   -   3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesulfonic        acid monosodium salt;    -   3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinnamic        acid and sodium salt;    -   2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;    -   2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;    -   4,6-bis(2,4-dimethylphenyl)-2-(4-(3-dodecyloxy*-2-hydroxypropoxy)-2-hydroxyphenyl)-s-triazine        (*is mixture of C₁₂₋₁₄oxy isomers);    -   12-hydroxy-3,6,9-trioxadodecyl        3-tert-butyl-4-hydroxy-5-(2H-benzotriazol-2-yl)-hydrocinnamate;    -   2,4-dihydroxybenzophenone;    -   2,2′-dihydroxy-4,4′-dimethoxy-5,5′-disulfobenzophenone, disodium        salt;    -   2,2′,4,4′-tetrahydroxybenzophenone;    -   3-(4-benzoyl-3-hydroxyphenoxy)-2-hydroxy-N,N,N-trimethyl-1-propanaminium        chloride;    -   3-[4-(2H-        benzotriazol-2-yl)-3-hydroxyphenoxy]-2-hydroxy-N,N,N-trimethyl-1-propanaminium,        chloride;    -   5-benzoyl-4-hydroxy-2-methoxy-benzenesulfonic acid, sodium salt;        and    -   2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole.

Additional suitable antioxidants are for example selected from thehindered phenolic and benzofuranone stabilizers.

Suitable antioxidants are for example selected from the group consistingof

The hindered amine light stabilizers (HALS) of component (c) are forexample known commercial compounds. They are for example selected fromthe group consisting of

-   -   bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,        bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate,        bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,        n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic        acid-bis(1,2,2,6,6-pentamethylpiperidyl)ester, the condensate of        1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and        succinic acid, the condensate of        N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine        and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,        tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,        tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetraoate,        1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),        4-benzoyl-2,2,6,6-tetramethylpiperidine,        4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(        1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,        3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,        the condensate of        N,N-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and        4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of        2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine        and 1,2-bis(3-aminopropylamino)ethane, the condensate of        2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine        and 1,2-bis(3-aminopropylamino)ethane,        8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,        3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,        3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)-pyrrolidine-2,5-dione,        a mixture of 4-hexadecyloxy- and        4-stearyloxy-2,2,6,6-tetramethylpiperidine, the condensate of        N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine        and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, the        condensate of 1,2-bis(3-aminopropylamino)ethane and        2,4,6-trichloro-1,3,5-triazine and        4-butylamino-2,2,6,6-tetramethylpiperidine (CAS reg. No.        [136504-96-6]);        (2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,        (1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,        2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane,        the reaction product of        7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane        and epichlorohydrin,        tetra(2,2,6,6-tetramethylpiperidin-4-yl)-butane-1,2,3,4-tetracarboxylate,        tetra(1,2,2,6,6-pentamethylpiperidin-4-yl)-butane-1,2,3,4-tetracarboxylate,        2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]        -heneicosan,        8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4,5]-decane-2,4-dione,        wherein m is a value from 5-50,

The complex formers of component (c) are for example nitrogen-containingcomplex formers or polyanionically-derived natural polysaccharides, forexample those containing phosphate, phosphonate or methylphosphonategroups, such as chitin derivatives, e.g. sulfochitin,carboxymethylchitin, phosphochitin or chitosan derivatives, for examplesulfochitosan, carboxymethylchitosan or phosphochitosan.

The complex formers are for example selected from the group consistingof ethylenediaminetetracetic acid (EDTA), nitrilotriacetic acid (NTA),β-alaninediacetic acid (EDETA) or ethylenediaminedisuccinic acid (EDDS),

aminetrimethylenephosphoric acid (ATMP) conforming to formula

serinediacetic acid (SDA) conforming to formula

asparaginediacetic acid conforming to formula

methylglycinediacetic acid (MGDA) conforming to formula

The present stabilizer systems are particularly suitable for stabilizingbody care products, in particular for use in skin-care products, as bathand shower products, preparations containing fragrances and odoriferoussubstances, hair-care products, dentifrices, deodorizing andantiperspirant preparations, decorative preparations, light protectionformulations and preparations containing active ingredients.

Suitable skin-care products are, in particular, body oils, body lotions,body gels, treatment creams, skin protection ointments, shavingpreparations, such as shaving foams or gels, skin powders, such as babypowder, moisturising gels, moisturising sprays, revitalising bodysprays, cellulite gels and peeling preparations.

Preparations containing fragrances and odoriferous substances are inparticular scents, perfumes, toilet waters and shaving lotions(aftershave preparations).

Suitable hair-care products are, for example, shampoos for humans andanimals, in particular dogs, hair conditioners, products for styling andtreating hair, perming agents, hair sprays and lacquers, hair gels, hairfixatives and hair dyeing or bleaching agents.

Suitable dentifrices are in particular tooth creams, toothpastes,mouth-washes, mouth rinses, anti-plaque preparations and cleaning agentsfor dentures.

Suitable decorative preparations are in particular lipsticks, nailvarnishes, eye shadows, mascaras, dry and moist make-up, rouge, powders,depilatory agents and suntan lotions.

Suitable cosmetic formulations containing active ingredients are inparticular hormone preparations, vitamin preparations, vegetable extractpreparations and antibacterial preparations.

The present body care products can be in the form of creams, ointments,pastes, foams, gels, lotions, powders, make-ups, sprays, sticks oraerosols. The present stabilizer systems may be present in the oil phaseor in the aqueous or aqueous/alcoholic phase.

The additives of component (b) are present, for example, in the bodycare and household products in a concentration of about 5 to about 10000ppm, based on the total formulation, for example from about 10 to about5000 ppm, for example from about 100 to about 1000 ppm. For example theadditives of component (b) are present in the body care and householdproducts in a concentration of about 5, 10, 15, 20, 25, 35, 40, 45 or 50ppm, based on the total formulation. For example, the additives ofcomponent (b) are present from about 5 to about 1000 ppm in theformulations (compositions) of this invention. These ppm concentrationsare parts by weight.

Laundry detergents, fabric softeners or other products, from which theadditives of component (b) are intended for deposition onto fabrics withuse, are considered household products of this invention, and the aboveconcentration levels also pertain thereto. The present additives ofcomponent (b) are effective at stabilizing the laundry detergents andfabric softeners, as well as the fabrics treated therewith.

Creams are oil-in-water emulsions containing more than 50% water. Theoil-containing base used therein is usually mainly fatty alcohols, forexample lauryl, cetyl or stearyl alcohol, fatty acids, for examplepalmitic or stearic acid, liquid to solid waxes, for exampleisopropylmyristate or beeswax and/or hydrocarbon compounds, such asparaffin oil. Suitable emulsifiers are surfactants having primarilyhydrophilic properties, such as the corresponding nonionic emulsifiers,for example fatty acid esters of polyalcohols of ethylene oxide adducts,such as polyglycerol fatty acid ester or polyoxyethylenesorbitan fattyacid ether (Tween trademarks); polyoxyethylene fatty alcohol ether ortheir esters or the corresponding ionic emulsifiers, such as the alkalimetal salts of fatty alcohol sulfonates, sodium cetyl sulfate or sodiumstearyl sulfate, which are usually used together with fatty alcohols,such as cetyl alcohol or stearyl alcohol. In addition, creams containagents which reduce water loss during evaporation, for examplepolyalcohols, such as glycerol, sorbitol, propylene glycol, and/orpolyethylene glycols.

Ointments are water-in-oil emulsions which contain up to 70%, forinstance not more than 20 to 50%, of water or of an aqueous phase. Theoil-containing phase contains predominantly hydrocarbons, such asparaffin oil and/or solid paraffin which for instance contains hydroxycompounds, for example fatty alcohol or their esters, such as cetylalcohol or wool wax for improving the water absorption. Emulsifiers arecorresponding lipophilic substances, such as sorbitan fatty acid ester.In addition, the ointments contain moisturisers such as polyalcohols,for example glycerol, propylene glycol, sorbitol and/or polyethyleneglycol as well as preservatives.

Rich creams are anhydrous formulations and are produced on the basis ofhydrocarbon compounds, such as paraffin, natural or partially syntheticfats, for example coconut fatty acid triglycerides or, for instance,hardened oils and glycerol partial fatty acid esters.

Pastes are creams and ointments containing powdered ingredients whichabsorb secretions, for example metal oxides, such as titanium dioxide orzinc oxide, and also tallow and/or aluminium silicates which bind themoisture or the absorbed secretion.

Foams are liquid oil-in-water emulsions in aerosol form. Hydrocarboncompounds are used, inter alia, for the oil-containing phase, forexample paraffin oil, fatty alcohols, such as cetyl alcohol, fatty acidesters, such as isopropylmyristate and/or waxes. Suitable emulsifiersare, inter alia, mixtures of emulsifiers having predominantlyhydrophilic properties, for example polyoxyethylenesorbitan fatty acidester, and also emulsifiers having predominantly lipophilic properties,for example sorbitan fatty acid ester. Commercially available additivesare usually additionally employed, for example preservatives.

Gels are, in particular, aqueous solutions or suspensions of activesubstances in which gel formers are dispersed or swelled, in particularcellulose ethers, such as methyl cellulose, hydroxyethyl cellulose,carboxymethyl cellulose or vegetable hydrocolloids, for example sodiumalginate, tragacanth or gum Arabic and polyacrylate thickener systems.The gels for example additionally contain polyalcohols, such aspropylene glycol or glycerol as moisturisers and wetting agents, such aspolyoxyethylenesobitan fatty acid ester. The gels furthermore containcommercially available preservatives, such as benzyl alcohol, phenethylalcohol, phenoxyethanol and the like.

The following is a list of examples of body care products of thisinvention and their ingredients: Body care product Ingredientsmoisturising cream vegetable oil, emulsifier, thickener, perfume, water,antioxidant, UV absorbers shampoo surfactant, emulsifier, preservatives,perfume, antioxidant, UV absorbers toothpaste cleaning agent, thickener,sweetener, flavor, colorant, antioxidant, water, UV absorbers lip-carestick vegetable oil, wax, TiO₂, antioxidant, UV absorbers

The present body care products, household products, textiles and fabricshave high stability towards color changes and chemical degradation ofthe ingredients present in these products. For example, presentcompositions that comprise a dye are found to have excellent colorstability.

Accordingly, the present invention further pertains to a stabilizedcomposition comprising

(a) a body care product, household product, textile or fabric,

(b) an effective stabilizing amount of at least one compound selectedfrom the group consisting of

-   -   (i) the dialkylhydroxylamine stabilizers,    -   (ii) the dialkylhydroxylamine stabilizer salts,    -   (iii) the nitrone stabilizers and    -   (iv) the amine oxide stabilizers and

(d) a dye.

The term “effective stabilizing amount” means for example the amountnecessary to achieve the desired dye stability.

Dyes according to the present invention are for example:

-   -   inorganic pigments, for example iron oxide (Iron Oxide Red, Iron        Oxide Yellow, Iron Oxide Black, etc.), Ultramarines, Chromium        Oxide Green or Carbon Black;    -   natural or synthetic organic pigments;    -   disperse dyes which may be solubilzed in solvents like direct        hair dyes of the HC type, for example HC Red No. 3, HC Blue No.        2 and all other hair dyes listed in International Cosmetic        Ingredient Dictionary and Handbook, 7^(th) edition 19997) or the        dispersion dyes listed in Color Index International or Society        of Dyers and Colourists;    -   color varnishes (insoluble salts of soluble dyes, like many Ca-,        Ba- or Al-salts of anionic dyes);    -   soluble anionic or cationic dyes, like acid dyes (anionic),        basic dyes (cationic), direct dyes, reactive dyes or solvent        dyes.

Generally, for the coloration of household- and body care products allsubstances are suitable which have an absorption in the visible light ofelectromagnetic radiation (wavelength of ca. 4000 to 700 nm). Theabsorption is often caused by the following chromophores: Azo- (mono-,di, tris-, or poly-)stilbene-, carotenoide-, diarylmethan-,triarylmethan-, xanthen-, acridin-, quinoline, methin- (alsopolymethin-), thiazol-, indamin-, indophenol-, azin-, oxazin, thiazin-,anthraquinone-, indigoid-, phtalocyanine- and further synthetic, naturaland/or inorganic chromophores.

The present stabilizer systems are also used in household cleaning andtreatment agents, for example in laundry products and fabric softeners,liquid cleansing and scouring agents, glass detergents, neutral cleaners(all-purpose cleaners), acid household cleaners (bath), bathroomcleaners, for instance in washing, rinsing and dishwashing agents,kitchen and oven cleaners, clear rinsing agents, dishwasher detergents,shoe polishes, polishing waxes, floor detergents and polishes, metal,glass and ceramic cleaners, textile-care products, rug cleaners andcarpet shampoos, agents for removing rust, color and stains (stainremover salt), furniture and multipurpose polishes and leather and vinyldressing agents (leather and vinyl sprays) and air fresheners.

The present invention also concerns home care and fabric care productssuch as drain cleaners, disinfectant solutions, upholstery cleaners,automotive care products (e.g., to clean and/or polish and protectpaint, tires, chrome, vinyl, leather, fabric, rubber, plastic andfabric), degreasers, polishes (glass, wood, leather, plastic, marble,granite, and tile, etc.), and metal polishes and cleaners. Antioxidantsare suitable to protect fragrances in above products as well as in dryersheets. The present invention also relates to home care products such ascandles, gel candles, air fresheners and fragrance oils (for the home).

The stabilizers of the present invention may be employed in fabrictreatment that takes place after use of the fabric, referred to asfabric care. Such treatments include laundering, which uses detergentsand/or fabric conditioner, and the application of non-detergent basedfabric care products, such as spray-on products. When employed in thisfashion, the present stabilizers are intended for deposition onto thefabric and used to protect the fabric, colorants and fragrancesassociated with said these fabrics from environmental damage.

Typical examples of household cleaning and treating agents are:Household cleaners/ household treating agents Ingredients detergentconcentrate surfactant mixture, ethanol, antioxidant, water, UVabsorbers, antioxidant shoe polish wax, wax emulsifier, antioxidant,water, preservative, UV absorbers, antioxidant wax-containing flooremulsifier, wax, sodium chloride, antioxidant, cleaning agent water,preservative, UV absorbers, antioxidant

The present stabilizers are for example incorporated by dissolution inan oil phase or alcoholic or water phase, where required at elevatedtemperature.

The present invention also pertains to a method of stabilizing a bodycare product, household product, textile or fabric, which comprisesincorporating therein or applying thereto at least one compound selectedfrom the group consisting of

(i) the dialkylhydroxylamine stabilizers,

(ii) the dialkylhydroxylamine stabilizer salts,

(iii) the nitrone stabilizers and

(iv) the amine oxide stabilizers.

In the case of stabilized fabrics, for example dyed fabrics, the presentstabilizers are applied thereto via deposition from for instancedetergents, fabric conditioners or non-detergent based fabric careproducts.

The present fabrics are natural or synthetic, and may be woven ornonwoven.

The present invention also pertains to a method of stabilizing a bodycare product, household product, textile or fabric, each of whichcontain a dye, which comprises incorporating therein or applying theretoat least one compound selected from the group consisting of components(i)-(iv). The present stabilizers of components (i)-(iv) are veryeffective towards the stabilization of dyes in the present compositions.

The textiles of this invention are for example textile fiber materials,for example nitrogen-containing or hydroxy-group-containing fibermaterials, for instance textile fiber materials selected from cellulose,silk, wool, synthetic polyamides, leather and polyurethanes. Includedare cotten, linen and hemp, pulp and regenerated cellulose. Includedalso are cellulosic blends, for example mixtures of cotton and polyamideor cotton/polyester blends.

The additives of the present invention are for example applied totextiles in a dyeing or printing process, or in a finishing process. Forinstance, the additives may be applied as part of a dye formulation. Theadditives may be applied to textiles for example in an ink-jet printingprocess. The additives are for example applied as part of an aqueous dyesolution or printing paste. They may be applied in an exhaust method ordyeing by the padder dyeing method, in which the textiles areimpregnated with aqueous dye solutions, which may contain salts, and thedyes and additives are fixed, after an alkali treatment or in thepresence of alkali, if appropriate with the action of heat or by storageat room temperature for several hours. After fixing, the dyeings orprints are rinsed thoroughly with cold and hot water, if appropriatewith the addition of an agent which has a dispersing action and promotesdiffusion of the non-fixed portions.

The dye or ink formulations for application to textiles may comprisefurther customary additves, for example surfactants, antifoams,antimicrobials and the like, for example as disclosed in U.S. Pat. Nos.6,281,339, 6,353,094 and 6,323,327, the disclosures of which are herebyincorporated by reference.

The following Examples illustrate the invention. Percentages are inweight percent unless indicated otherwise.

EXAMPLE 1

The instant compound is obtained from Aldrich Chemical Company.

EXAMPLE 2

The instant compound is obtained from Aldrich Chemical Company.

EXAMPLE 3

The instant compound is obtained from Aldrich Chemical Company.

EXAMPLE 4

Example 3 (3.2 g, 0.012 mole) is dissolved in 50 mL of anhydrousisopropanol. To this stirred solution is added dropwise 1.5 mL ofabsolute isopropanol (7.60 molar hydrochloric acid) at 40 C. Afterthirty minutes, the mixture is heated to 50 C. for thirty minutes. Theresulting clear solution is cooled to 5 C. The resulting whiteprecipitate is filtered, washed with cold isopropanol, and dried toconstant weight in a vacuum oven. The title compound is received (3.4 g,92% yield) as a white solid with a melting point of 161-169° C. whosestructure is consistent with HNMR.

EXAMPLE 5

Example 2 (8.9 g, 0.1 mole) is dissolved in 100 mL of anhydrousdiethylether. To this stirred solution is added dropwise 59 mL ofabsolute ethanol (1.68 molar hydrochloric acid) at ambient temperature.After three hours, the solvent is removed by distillation and replacedwith 25 mL of isopropanol/hexane (1:2 ratio). The resulting whiteprecipitate is filtered, washed with cold isopropanol/hexane (1:2ratio), and dried to constant weight in a vacuum oven. The titlecompound is received (5.2 g, 43% yield) as a white solid with a meltingpoint of 70-72 C whose structure is consistent with HNMR.

EXAMPLE 6

Example 1 (10.7 g, 0.05 mole) is dissolved in 35 mL of heptane and 35 mLof anhydrous isopropanol. To this stirred solution is added dropwise9.38 g of absolute isopropanol containing 0.05 mole of hydrochloric acidat ambient temperature. The resulting white precipitate is filtered,recrystallized from 400 g of boiling isopropanol, and dried to constantweight in a vacuum oven. The title compound is received (8.5 g, 68%yield) as a white solid with a melting point of 174 C. whose structureis consistent with HNMR.

EXAMPLE 7

The instant compound is prepared according to J. E. Baldwin,Tetrahedron, 1984, 40(21), 4363-70.

EXAMPLE 8

The instant compound is prepared according to J. E. Baldwin,Tetrahedron, 1984, 40(21), 4363-70.

EXAMPLE 9

The instant compound is prepared according to J. E. Baldwin,Tetrahedron, 1984, 40(21), 4363-70.

EXAMPLE 10

The instant compound is prepared according to U.S. Pat. No. 4,898,901.

EXAMPLE 11

The instant compound is prepared according to U.S. Pat. No. 4,898,901.

EXAMPLE 12

The instant compound is prepared according to U.S. Pat. No. 4,972,009and U.S. Pat. No. 5,202,441.

EXAMPLE 13

The instant compound is prepared according to U.S. Pat. No. 4,898,901.

EXAMPLE 14

The instant compound is prepared according to U.S. Pat. No. 4,898,901.

EXAMPLE 16

The instant compound is prepared according to U.S. Pat. No. 4,898,901.

EXAMPLE 17

The instant compound is prepared according to U.S. Pat. Nos. 5,081,300,5,162,408, 5,844,029, 5,880,191, and 5,922,794.

EXAMPLE 18

The instant compounds are added to a commercial shampoo formulation andare evaluated for their ability to reduce the amount of dye fading whenthe samples are exposed to fluorescent lighting. The instant compounds(0.36 g) are dissolved in 5 mL of methanol which is then added to 120 gof shampoo (Suave® Natural Fresh Mountain Strawberry Shampoo) withagitation. The stabilized shampoo formulation is agitated for 15 minutesand put into 20 mL glass scintillation vials. These formulations areweathered under fluorescent light aging at ambient temperature. TheCIEL*a*b coordinates before and after exposure are measured using X-Rite938 Spectrodensitometer. Color change is expressed as Delta E (DE). Thecolor change is given by Delta E (DE) which is calculated by:DE=[(DL*)²+(Da*)²+(Db*)²]^(1/2) Stabilizer DE after (loading at 0.30 wt%) 2 weeks None 8.49 Example 9 7.38 Example 2 7.26 Example 5 6.44Example 7 5.13 Example 6 4.61 Example 8 4.46

compounds according to this invention are able to improve clearly thelight fastness of shampoo formulations.

EXAMPLE 19

The instant compounds are added to a commercial shampoo formulation andare evaluated for their ability to reduce the amount of dye fading whenthe samples are exposed to fluorescent lighting. The instant compounds(0.36 g) are dissolved in 5 mL of methanol which is then added to 120 gof shampoo (Clairol® Herbal Essences Shampoo) with agitation. Thestabilized shampoo formulation is agitated for 15 minutes and put into20 mL glass scintillation vials. These formulations are weathered underfluorescent light aging at ambient temperature. The CIEL*a*b coordinatesbefore and after exposure are measured using X-Rite 938Spectrodensitometer. Color change is expressed as Delta E (DE).Stabilizer DE after (loading at 0.30 wt %) 2 weeks None 1.86 Example 81.40 Example 5 1.22

The compounds according to this invention are able to improve clearlythe light fastness of shampoo formulations.

EXAMPLE 20

The instant compounds are added to a commercial mouthwash formulationand are evaluated for their ability to reduce the amount of dye fadingwhen the samples are exposed to fluorescent lighting. The instantcompounds (0.36 g) are dissolved in 5 mL of methanol which is then addedto 120 g of mouthwash (Scope® Original Mint) with agitation. Thestabilized mouthwash formulation is agitated for 15 minutes and put into20 mL glass scintillation vials. These formulations are weathered underfluorescent light aging at ambient temperature. The CIEL*a*b coordinatesbefore and after exposure are measured using X-Rite 938Spectrodensitometer. Color change is expressed as Delta E (DE).Stabilizer DE after (loading at 0.30 wt %) 2 weeks None 5.30 Example 55.02 Example 8 2.28

The compounds according to this invention are able to improve clearlythe light fastness of mouthwash formulations.

EXAMPLE 21

The instant compounds are added to a commercial mouthwash formulationand are evaluated for their ability to reduce the amount of dye fadingwhen the samples are exposed to fluorescent lighting. The instantcompounds (0.36 g) are dissolved in 5 mL of methanol which is then addedto 120 g of mouthwash (Listerine® Cool Mint) with agitation. Thestabilized mouthwash formulation is agitated for 15 minutes and put into20 mL glass scintillation vials. These formulations are weathered underfluorescent light aging at ambient temperature. The CIEL*a*b coordinatesbefore and after exposure are measured using X-Rite 938Spectrodensitometer. Color change is expressed as Delta E (DE).Stabilizer DE after (loading at 0.30 wt %) 7 weeks None 2.70 Example 92.64 Example 8 2.04 Example 5 0.91 Example 2 0.64

The compounds according to this invention are able to improve clearlythe light fastness of mouthwash formulations.

EXAMPLE 22

The instant compounds are added to a commercial shampoo formulation andare evaluated for their ability to reduce the amount of dye fading whenthe samples are exposed to fluorescent lighting. The instant compoundsare dissolved in a shampoo formulation with agitation.3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesulfonicacid monosodium salt, a benzotriazole UV absorber, is added to theshampoo formulation. These formulations are weathered under fluorescentlight at ambient temperature. The CIEL*a*b coordinates before and afterexposure are measured. The change in color is expressed by Delta E (DE).The compounds according to this invention are quite efficacious inimproving light fastness of shampoo formulations.

EXAMPLE 23

The instant compounds are added to a commercial shampoo formulation andare evaluated for their ability to reduce the amount of dye fading whenthe samples are exposed to fluorescent lighting. The instant compoundsare dissolved in a shampoo formulation with agitation. A s-triazine UVabsorber is added to the shampoo formulation. These formulations areweathered under fluorescent light at ambient temperature. The CIEL*a*bcoordinates before and after exposure are measured. The change in coloris expressed by Delta E (DE). The compounds according to this inventionare quite efficacious in improving light fastness of shampooformulations.

EXAMPLE 24

The instant compounds are added to a commercial shampoo formulation andare evaluated for their ability to reduce the amount of dye fading whenthe samples are exposed to fluorescent lighting. The instant compoundsare dissolved in a shampoo formulation with agitation. A benzophenone UVabsorber is added to the shampoo formulation. These formulations areweathered under fluorescent light at ambient temperature. The CIEL*a*bcoordinates before and after exposure are measured. The change in coloris expressed by Delta E (DE). The compounds according to this inventionare quite efficacious in improving light fastness of shampooformulations.

EXAMPLE 25

The instant compounds are added to a commercial mouthwash formulationand are evaluated for their ability to reduce the amount of dye fadingwhen the samples are exposed to fluorescent lighting. The instantcompounds are added to a mouthwash formulation with agitation.3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesulfonicacid monosodium salt, a benzotriazole UV absorber, is added to themouthwash formulation. These formulations are weathered underfluorescent lighting at ambient temperature. The CIEL*a*b coordinatesbefore and after exposure are measured. Color change is expressed asDelta E (DE). The compounds according to this invention are quiteefficacious in improving light fastness of mouthwash formulations.

EXAMPLE 26

The instant compounds are added to a commercial mouthwash formulationand are evaluated for their ability to reduce the amount of dye fadingwhen the samples are exposed to fluorescent lighting. The instantcompounds are added to a mouthwash formulation with agitation. Ans-triazine UV absorber is added to the mouthwash formulation. Theseformulations are weathered under fluorescent lighting at ambienttemperature. The CIEL*a*b coordinates before and after exposure aremeasured. Color change is expressed as Delta E (DE). The compoundsaccording to this invention are quite efficacious in improving lightfastness of mouthwash formulations.

EXAMPLE 27

The instant compounds are added to a commercial mouthwash formulationand are evaluated for their ability to reduce the amount of dye fadingwhen the samples are exposed to fluorescent lighting. The instantcompounds are added to a mouthwash formulation with agitation. Abenzophenone UV absorber is added to the mouthwash formulation. Theseformulations are weathered under fluorescent lighting at ambienttemperature. The CIEL*a*b coordinates before and after exposure aremeasured. Color change is expressed as Delta E (DE). The compoundsaccording to this invention are quite efficacious in improving lightfastness of mouthwash formulations.

EXAMPLE 28

An aqueous based test formulation is prepared as follows: sodium laurethsulfate (30%, TEXAPON NSO, Cognis) 30% cocamidopropylbetaine (30%,DEHYTON K, Cognis) 10% colorant* 0.001%   instant stabilizer 0.05%  citric acid (10% aqueous solution) to pH 6 deionized water to 100%*Colorant is PURICOLOR BLUE ABL9 (FD&C Blue No. 1)

About 20 mL of each of the aqueous test formulations are placed in aborosilicate glass bottle. The glass bottles are exposed in an AtlasCi-65 Xenon arc WeatherOmeter, AATCC Test Method 16. Color measurementsare performed on a Hunter Ultrascan XE spectrophotometer. Delta L, a andb values are the difference between the initial values and the values ateach interval. It is seen that the stabilizers of the present inventionprovide excellent color stability in personal care products.

EXAMPLE 29

An aqueous based test formulation is prepared as follows: sodium laurethsulfate (30%, TEXAPON NSO, Cognis) 30% cocamidopropylbetaine (30%,DEHYTON K, Cognis) 10% colorant* 0.001%   instant stabilizer 0.05%  citric acid (10% aqueous solution) to pH 6 deionized water to 100%*Colorant is PURICOLOR RED ARE33 (FD&C Red No. 33).

About 20 mL of each of the aqueous test formulations are placed in aborosilicate glass bottle. The glass bottles are exposed in an AtlasCi-65 Xenon arc WeatherOmeter, AATCC Test Method 16, option E. Colormeasurements are performed on a Hunter Ultrascan XE spectrophotometer.Delta L, a and b values are the difference between the initial valuesand the values at each interval. It is seen that the stabilizers of thepresent invention provide excellent color stability in personal careproducts.

EXAMPLE 30

An aqueous based test formulation is prepared as follows: sodium laurethsulfate (30%, TEXAPON NSO, Cognis) 30% cocamidopropylbetaine (30%,DEHYTON K, Cognis) 10% colorant* 0.001%   instant stabilizer 0.05%  citric acid (10% aqueous solution) to pH 6 deionized water to 100%*Colorant is FD&C Red No. 40.

About 20 mL of each of the aqueous test formulations are placed in aborosilicate glass bottle. The glass bottles are exposed in an AtlasCi-65 Xenon arc WeatherOmeter, AATCC Test Method 16. Color measurementsare performed on a Hunter Ultrascan XE spectrophotometer. Delta L, a andb values are the difference between the initial values and the values ateach interval. It is seen that the stabilizers of the present inventionprovide excellent color stability in personal care products.

EXAMPLE 31

An aqueous based test formulation is prepared as follows: sodium laurethsulfate (30%, TEXAPON NSO, Cognis) 30% cocamidopropylbetaine (30%,DEHYTON K, Cognis) 10% colorant* 0.001%   instant stabilizer 0.05%  citric acid (10% aqueous solution) to pH 6 deionized water to 100%*Colorant is PURICOLOR BLUE ABL9 (FD&C Blue No. 1)

About 20 mL of each of the aqueous test formulations are placed in aborosilicate glass bottle. The glass bottles are also exposed toaccelerated fluorescent lighting, Philips, 40 Watt, Daylight Deluxe(D65), full exposure to light. Color measurements are performed on aHunter Ultrascan XE spectrophotometer. Delta L, a and b values are thedifference between the initial values and the values at each interval.It is seen that the stabilizers of the present invention provideexcellent color stability in personal care products.

EXAMPLE 32

An aqueous based test formulation is prepared as follows: sodium laurethsulfate (30%, TEXAPON NSO, Cognis) 30% cocamidopropylbetaine (30%,DEHYTON K, Cognis) 10% colorant* 0.001%   instant stabilizer 0.05%  citric acid (10% aqueous solution) to pH 6 deionized water to 100%*Colorant is PURICOLOR RED ARE33 (FD&C Red No. 33).

About 20 mL of each of the aqueous test formulations are placed in aborosilicate glass bottle. The glass bottles are also exposed toaccelerated fluorescent lighting, Philips, 40 Watt, Daylight Deluxe(D65), full exposure to light. Color measurements are performed on aHunter Ultrascan XE spectrophotometer. Delta L, a and b values are thedifference between the initial values and the values at each interval.It is seen that the stabilizers of the present invention provideexcellent color stability in personal care products.

EXAMPLE 33

An aqueous based test formulation is prepared as follows: sodium laurethsulfate (30%, TEXAPON NSO, Cognis) 30% cocamidopropylbetaine (30%,DEHYTON K, Cognis) 10% colorant* 0.001%   instant stabilizer 0.05%  citric acid (10% aqueous solution) to pH 6 deionized water to 100%*Colorant is FD&C Red No. 40.

About 20 mL of each of the aqueous test formulations are placed in aborosilicate glass bottle. The glass bottles are also exposed toaccelerated fluorescent lighting, Philips, 40 Watt, Daylight Deluxe(D65), full exposure to light. Color measurements are performed on aHunter Ultrascan XE spectrophotometer. Delta L, a and b values are thedifference between the initial values and the values at each interval.It is seen that the stabilizers of the present invention provideexcellent color stability in personal care products.

EXAMPLE 34 Moisturizer Cream

The components of phase A are thoroughly mixed in a homogenizer for 10min at 75-80° C. The water phase B, likewise heated to 75-80° C.beforehand, is slowly added and the mixture is homogenized for 1 min.The mixture is cooled, with stirring, to 40° C. and then phases C and Eare added and the mixture is homogenized for 1 min. Subsequently, phaseD is added and the mixture is homogenized for ½ min and cooled, withstirring, to room temperature. Phase Ingredients (w/w) % A passionfloweroil 8 glyceryl dioleate 4 dicapryl ether 4 Isopropylisostearate 4instant stabilizer 0.05 B water, demin. ad. 100 EDTA 0.1 C Carbomer 0.15D sodium hydroxide 10% 0.20 E perfume; preservative q.s.

It is seen that the stabilizers of the present invention provideexcellent color stability in personal care products.

EXAMPLE 35 Toilet Water

The components below are thoroughly mixed in the cited sequence at 50°C., a clear homogeneous solution being obtained. The UV absorber is, forexample,3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesulfonicacid monosodium salt. Ingredients (w/w) % ethanol, 96% 60 d-limonene 5cedrene 1.5 citronellol 0.5 savin 0.5 instant stabilizer 0.08 UVabsorber 0.1 S,S-EDDS 0.005 colorant (D&C Yellow No. 5) 0.02 water ad.100Excellent results are achieved for this example of a toilet waterformulation.

EXAMPLE 36 Hair Styling Spray

The hydroxypropyl cellulose is first predissolved in half of the alcohol(Vortex mixer) and is charged with the aminomethylpropanol. The othercomponents—with the exception of the acrylate resin—are dissolved inalcohol and this solution is added, with stirring, to the hydroxypropylcellulose. Subsequently, the acrylate resin is added and stirred untilcompletely dissolved. The UV absorber used is, for example,benzophenone-4 is 5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid,sodium salt. Ingredients (w/w) % alcohol, anhydrous 96.21octylacrylamide/acrylate/butylaminoethylmethacrylate 2.52 copolymerhydroxypropyl cellulose 0.51 aminomethylpropanol (95%) 0.46 instantstabilizer 0.05 UV absorber 0.05 perfume oil 0.20

EXAMPLE 37 Shampoo for Greasy Hair

The components listed below are mixed, with stirring, at roomtemperature until they are completely dissolved. The pH is 6.5. The UVabsorber is, for example,2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole. Ingredients(w/w) % sodium myreth sulfate 50.00 TEA abietoyl collagen hydrolysate3.50 laureth-3 3.00 colorant (D&C Red No. 33) 0.20 instant stabilizer0.05 UV absorber 0.15 phosphonomethylchitosan, sodium salt 0.01 perfumeoil 0.10 water ad. 100

Excellent results are achieved for this example of a shampoo compositionfor oily hair.

EXAMPLE 38 Leather Dressing and Cleaning Agent

The stabilizer is predissolved in the terpene. The components are thenstirred in the cited sequence at about 65° C. until homogeneous. Themixture is then cooled to room temperature. Ingredients (w/w) %synthetic soap (Zetesap 813) 7.85 Glycerol 6.00 anionic surfactant(Lumorol 4192; Mulsifan RT 13) 22.00 Vaseline 11.00 paraffin 52/54 20.00Talcum 2.00 orange terpene 4.00 instant stabilizer 0.02 Water 27.13

Excellent results are achieved for this example of a leather dressingand cleaning agent composition.

EXAMPLE 39 Glass Detergent

The components listed below are dissolved in the cited sequence until aclear homogeneous mixture is obtained. Ingredients (w/w) %anionic/amphoteric surfactants (Lumorol RK) 0.7 butyl glycol 5.0Isopropanol 20.0 d-limonene 4.00 instant stabilizer 0.02 water, demin.ad. 100Excellent results are achieved for this example of a glass detergentformulation.

EXAMPLE 40 Protection of Dyes in Fabrics

The instant stabilizers are each deposited (from water) on a dyed cottonfabric at 0.05, 0.1, 0.2, 0.5 and 1.0 percent by weight, based on theweight of the cotton. The dyed fabrics contain the following dyes at0.05, 0.1, 0.2 and 0.5 percent by weight based on cotton. This resultsin 60 separate formulations for each dye listed:

-   -   Scarlet HE-3G    -   Crimson HE-XL    -   Yellow HE-6G    -   Red HE-XL    -   Blue HE-XL    -   Turquoise H-A    -   Navy HE-XL    -   Remazol    -   Red RB    -   Brilliant Red RBS    -   Orange FR    -   Navy CG    -   Turquoise G    -   Black B

The cotton fabrics are subjected to light exposure in an Atlas Ci-65Xenon arc WetherOmeter or to accelerated fluorescent lighting. Thepresent stabilizers provide outstanding color protection to the dyedfabrics. This experiment simulates dye protection achievable throughdeposition of the present stabilizers via treatment with, for example,stabilizer-containing laundry detergent or fabric conditioner.

EXAMPLE 41 Protection of Dyes in Fabrics

The instant stabilizers and UV absorbers, for example3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-benzenesulfonicacid monosodium salt, are each deposited (from water) on a dyed cottonfabric at 0.05, 0.1, 0.2, 0.5 and 1.0 percent by weight, based on theweight of the cotton. The dyed fabrics contain the following dyes at0.05, 0.1, 0.2 and 0.5 percent by weight based on cotton. This resultsin 60 separate formulations for each dye listed:

-   -   Scarlet HE-3G    -   Crimson HE-XL    -   Yellow HE-6G    -   Red HE-XL    -   Blue HE-XL    -   Turquoise H-A    -   Navy HE-XL    -   Remazol    -   Red RB    -   Brilliant Red RBS    -   Orange FR    -   Navy CG    -   Turquoise G    -   Black B

The cotton fabrics are subjected to light exposure in an Atlas Ci-65Xenon arc WetherOmeter or to accelerated fluorescent lighting. Thepresent stabilizers provide outstanding color protection to the dyedfabrics. This experiment simulates dye protection achievable throughdeposition of the present stabilizers via treatment with for examplestabilizer-containing laundry detergent or fabric conditioner.

1. An article of manufacture comprising (a) a fabric and, depositedthereon, (b) an effective stabilizing amount of at least one compoundselected from dialkylhydroxylamine stabilizer salts, saiddialkylhydroxylamine stabilizer salts are of the formula(R₁R₂N—OH).(HY) where R₁ is alkyl of 1 to 36 carbon atoms, cycloalkyl of5 to 12 carbon atoms or aralkyl of 7 to 9 carbon atoms; or R₁ is saidalkyl, cycloalkyl or aralkyl substituted by one to six alkyl of 1 to 12carbon atoms, halogen, cyano, E₁O—, E₁CO—, E₁OCO—, E₁COO—, E₁S—, E₁SO—,E₁SO₂—, —NH₂, —NHE₁, —NE₁E₂, —PO(OE₁)(OE₂) or —OPO(OE₁)(OE₂) groups; R₂is hydrogen or independently has the same meaning as R₁, where at leastone of R₁ and R₂ contains a hydrogen alpha to the —NOH moiety; or R₁ andR₂ together form a C₂₋₁₂heterocyclic ring which contains at least onecarbon substituted hydrogen alpha to the —NOH moiety, where saidC₂₋₁₂heterocyclic ring is unsubstituted or is substituted by one tothree alkyl of 1 to 12 carbon atoms, halogen, cyano, E₁O—, E₁CO—,E₁OCO—, E₁COO—, E₁S—, E₁SO—, E₁SO₂—, —NH₂, —NHE₁, —NE₁E₂, —PO(OE₁)(OE₂)or —OPO(OE₁)(OE₂) groups; or where said C₂₋₁₂heterocyclic ring isinterrupted by one to three —O—, —NE₁—, —CO—, —CONE₁—, —S—, —SO—, —SO₂—,—COO—, —PO₃— or —PO₄E₁ groups; or where said heterocyclic ring is bothsubstituted and interrupted by said groups; E₁ and E₂ independently arehydrogen, alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atomssubstituted by one to three hydroxyl groups; or E₁ and E₂ independentlyare an oligomer of poly(ethylene glycol) or poly(propylene glycol)terminated by hydroxyl, methoxy, acetate or propionate, where theoligomer has a molecular weight up to about 500; and HY is an inorganicor organic acid, wherein Y is phosphate, phosphonate, carbonate,bicarbonate, nitrate, chloride, bromide, bisulfite, sulfite, bisulfate,sulfate, borate, formate, acetate, benzoate, citrate, oxalate, tartrate,acrylate, polyacrylate, fumarate, maleate, itaconate, glycolate,gluconate, malate, mandelate, tiglate, ascorbate, polymethacrylate, acarboxylate of nitrilotriacetic acid (NTA),diethylenetriaminepentamethylenephosphonic acid (DTPMPA),hydroxyethylethylenediaminetriacetic acid (HEDTA),ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaaceticacid (DTPA), diethylenediaminetetraacetic acid or ofdiethylenetriaminepentaacetic acid, an alkylsulfonate or anarylsulfonate.
 2. An article according to claim 1 where Y is chloride,bisulfate, sulfate, phosphate, nitrate, ascorbate, formate, acetate,benzoate, oxalate, citrate, a carboxylate of ethylenediaminetetraaceticacid, a carboxylate of diethylenetriaminepentaacetic acid, orpolyacrylate.
 3. An article according to claim 2 where Y is chloride,bisulfate or citrate.
 4. An article according to claim 1 in which thedialkylhydroxylamine stabilizer salts are selected from the groupconsisting of HY salts of N,N-dibenzylhydroxylamine,N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine,N,N-bis(2-hydroxypropyl)hydroxylamine,N,N-bis(3-hydroxypropyl)hydroxylamine,N,N-bis(2-carboxyethyl)hydroxylamine,N,N-bis(benzylthiomethyl)hydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-didodecylhydroxylamine,N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine,N,N-dioctadecylhydroxylamine, N-hexadecyl-N-tetradecylhydroxylamine,N-hexadecyl-N-heptadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine,N-methyl-N-octadecylhydroxylamine, N,N-di(hydrogenatedtallow)hydroxylamine, N


5. An article according to claim 4 in which the dialkylhydroxylaminestabilizer salts are HY salts of N,N-diethylhydroxylamine,N,N-bis(2-hydroxypropyl)hydroxylamine,N,N-bis(3-hydroxypropyl)hydroxylamine, N,N-dibenzylhydroxylamine, orN,N-di(hydrogenated tallow)hydroxylamine.
 6. An article according toclaim 5 in which the dialkylhydroxylamine stabilizer salts are HY saltsof N,N-diethylhydroxylamine or N,N-dibenzylhydroxylamine.
 7. An articleaccording to claim 1 further comprising (c) at least one compoundselected from the group consisting of ultraviolet light absorbers,antioxidants, tocopherol, tocopherol acetate, hindered amine lightstabilizers, complex formers, optical brighteners, surfactants, andpolyorganosiloxanes.
 8. An article according to claim 7 where theultraviolet light absorbers are selected from the group consisting of2H-benzotriazoles, s-triazines, benzophenones, α-cyanoacrylates,oxanilides, benzoxazinones, benzoates and α-alkyl cinnamates.
 9. Anarticle according to claim 1 further comprising (d) a dye.
 10. Anarticle according to claim 1 where the dialkylhydroxylamine stabilizersalt compounds are present on the fabric in a concentration of about 5ppm to about 10000 ppm based on the total weight of the fabric.
 11. Anarticle according to claim 10 where the dialkylhydroxylamine saltcompounds are present in a concentration of about 10 ppm to about 5000ppm based on the total weight of the fabric.